Homoallylic alcohols undergo smooth coupling with a variety of aldehydes in the presence of CeCl(3)(.)7H(2)O-LiI reagent system in refluxing dichloroethane under neutral conditions to produce the corresponding 4-iodotetrahydropyran derivatives in high yields. The spirocyclic-4-iodotetrahydropyrans are obtained in case of cyclic ketones.